Production of N-aryl-2-lactam and N-alkyl-2-lactam by reductive amination of lactones with aryl and alkyl nitro compounds

ABSTRACT

This invention relates to a process for producing N-aryl-2-lactams, N-alkyl-2-lactams, and N-cycloalky-2-lactams by reductive amination of lactones with aryl or alkyl nitro compounds utilizing a metal catalyst, which is optionally supported.

FIELD OF THE INVENTION

This invention relates to a process for producing N-aryl-2-lactams,N-alkyl-2-lactams, and N-cycloalkyl-2-lactams by reductive amination oflactones with aryl or alkyl nitro compounds utilizing a metal catalyst,which is optionally supported.

BACKGROUND OF THE INVENTION

Lactams, and particularly pyrrolidones, are important constituents inmany industrial applications, including as solvents in chemicalreactions, components in ink and coating formulations, coating strippersin the electronics industry, formulating agents in crop protectionproducts, and as intermediates in the production of pharmaceuticals. Forexample, N-cyclohexyl-2-pyrrolidone is used as a solvent or intermediatein many industrial applications, including the electronics industry(photo-resist stripping solutions), industrial cleaners, oil/gas wellmaintenance, and fiber dyeing. N-[2-hydroxyethyl]-2-pyrrolidone isuseful in industrial cleaning, printing inks, and gasoline and oiladditives. N-octyl-2-pyrrolidone is useful, for example, in themanufacture of agricultural products, as a detergent and dispersant, inindustrial and metal cleaners, in printing inks and in fiber dyeing.

Pyrrolidone derivatives are generally prepared on an industrial scale bythe catalytic or non-catalytic reaction of gamma butyrolactone with analkyl amine or ammonia. For example, U.S. Pat. No. 4,824,967 describes avapor phase process for the production of 2-pyrrolidone usingγ-butyrolactone and ammonia at a temperature of 230-300° C. and apressure of 0.35 MPa to 2.1 MPa. A magnesium silicate catalyst is usedwhich needs to be separated and regenerated following the reaction, andwhich may trap considerable amounts of the product. U.S. Pat. No.5,393,888 describes a liquid-phase process for producing 2-pyrrolidonefrom γ-butyrolactone and ammonia in the absence of a catalyst, but athigh temperature and pressure; the reaction is carried out at 200-375°C. and 4.8 to 12.4 MPa. In U.S. Pat. No. 6,348,601, methanol is reactedwith ammonia in the presence of a catalyst, and the resultant mixture ofmethyl amines is reacted with γ-butyrolactone to formN-methyl-2-pyrrolidone. The reaction temperatures are 300-500° C. andthe pressures are 0.8 to 3.6 MPa. U.S. Pat. No. 6,248,902 describes aliquid-phase, non-catalytic process for the production ofN-methyl-pyrrolidone from γ-butyrolactone and monomethylamine.

Aryl compounds have also been used as the amine in reactions withlactones. For example, U.S. Pat. No. 3,775,431 describes the synthesisof N-phenyl-γ-methyl-γ-butyrolactam from γ-methyl-butyrolactone andaniline in a reaction that is carried out at a temperature of 250° C.under a nitrogen atmosphere. U.S. Pat. No. 5,538,985 describes thesynthesis of 1-(4-chlorophenyl)-2-pyrrolidone from a reaction ofp-chloroaniline and γ-butyrolactone in the presence of hydrochloricacid; the reaction was carried out for 17 hours at temperatures up to140° C.; the product was recovered in a multi-step process. U.S. Pat.No. 6,350,883 describes a gas-phase process for reacting lactones withamines or ammonia in the presence of aluminosilicate zeolites to producelactams; the reactions are carried out at 180-400° C. and 0 to 1 MPa.

An efficient and low cost process for the production of aryl, alkyl andcycloalkyl lactams would be advantageous. The reactions described abovedo not use nitro compounds. Disclosed herein is a novel, one-stepprocess for converting lactones to aryl, alkyl and cycloalkyl lactamsusing nitro compounds in the presence of catalysts.

SUMMARY OF THE INVENTION

The present invention relates to a process for preparing N-aryl-2-lactam(III), N-cycloalkyl-2-lactam (IV), or a mixture thereof, which comprisesthe step of contacting a lactone (I) with an aryl nitro compound (II) inthe presence of a catalyst and hydrogen gas;

wherein:

(i) n=-11;

(ii) R₁, R₂, R₃, R₄, R₅ and R₆ taken independently are hydrogen,hydrocarbyl or substituted hydrocarby), C₁ to C₁₈ unsubstituted orsubstituted alkyl, unsubstituted or substituted alkenyl, unsubstitutedor substituted cycloalkyl, unsubstituted or substituted cycloalkylcontaining at least one heteroatom, unsubstituted or substituted aryl,and unsubstituted or substituted heteroaryl;

(iii) R₇ is an aromatic group having from 6 to 30 carbons, and R₈ is afully or partially reduced derivative of R₇.

(iv) N-aryl-2-lactam (III), N-cycloalkyl-2-lactam (IV), or a mixturethereof, may comprise 100% by weight of the total product formed, orwherein additional products may be produced; and

(v) the catalyst is selected from metals from the group consisting ofpalladium, ruthenium, rhenium, rhodium, iridium, platinum, nickel,cobalt, copper, iron, osmium; compounds thereof; and combinationsthereof.

The present invention also relates to a process for preparingN-alkyl-2-lactam (VI) which comprises the step of contacting a lactone(I) with an alkyl nitro compound (V) in the presence of a catalyst andhydrogen gas;

wherein:

(i) n=0-11;

(ii) R₁, R₂, R₃, R₄, R₅ and R₆ taken independently are hydrogen,hydrocarbyl or substituted hydrocarbyl, C₁ to C₁₈ unsubstituted orsubstituted alkyl, unsubstituted or substituted alkenyl, unsubstitutedor substituted cycloalkyl, unsubstituted or substituted cycloalkylcontaining at least one heteroatom, unsubstituted or substituted aryl,and unsubstituted or substituted heteroaryl;

(iii) R₉ is an alkyl group having from 1 to 30 carbons, and wherein R₉may be C₁-C₃₀ unsubstituted or substituted alkyl, C₁-C₃₀ unsubstitutedor substituted alkenyl, C₁-C₃₀ unsubstituted or substituted alkynyl,C₃-C₃₀ unsubstituted or substituted cycloalkyl, or C₃-C₃₀ unsubstitutedor substituted cycloalkyl containing at least one heteroatom;

(iv) N-alkyl-2-lactam (VI) may comprise 100% by weight of the totalproduct formed, or wherein additional products may be produced; and

(v) the catalyst is selected from metals from the group consisting ofpalladium, ruthenium, rhenium, rhodium, iridium, platinum, nickel,cobalt, copper, iron, osmium; compounds thereof; and combinationsthereof.

DETAILED DESCRIPTION OF THE INVENTION

By “aryl nitro compound” is meant the compound having the formula R—NO₂wherein R is an aromatic group.

“Heteroaryl” refers to unsaturated rings of 5 or 6 atoms containing oneor two O and S atoms and/or one to four N atoms provided that the totalnumber of hetero atoms in the ring is 4 or less, or bicyclic ringswherein the five or six membered ring containing O, S, and N atoms asdefined above is fused to a benzene or pyridyl ring. Common examples arefuran and thiophene.

By “catalyst” is meant a substance that affects the rate of the reactionbut not the reaction equilibrium, and emerges from the processchemically unchanged.

By “metal catalyst” is meant a catalyst that is comprised of at leastone metal, at least one Raney metal, compounds thereof or combinationsthereof.

By “promoter” is meant an element of the Periodic Table that is added toenhance the physical or chemical function of the catalyst. The promotercan also be added to retard undesirable side reactions and/or affect therate of the reaction.

By “metal promoter” is meant a metallic compound that is added toenhance the physical or chemical function of a catalyst. The metalpromoter can also be added to retard undesirable side reactions and/oraffect the rate of the reaction.

By “fully or partially reduced derivative” of an aryl compound is meanta compound that can be derived from the parent compound by saturating orreducing one or more of the unsaturated bonds in the aromatic ring.Unsaturated compounds are compounds that contain one or more carbon tocarbon double or triple bonds. For example, a fully reduced derivativeof a phenyl group is a cyclohexyl group.

This invention relates to the synthesis of 5-methyl-N-aryl-2-lactam(III), 5-methyl-N-cycloalkyl-2-lactam (IV) or a mixture thereof, from areaction between a lactone (I) and an aryl nitro compound (II) in thepresence of a catalyst and hydrogen gas;

wherein:

(i) n=0-11;

(ii) R₁, R₂, R₃, R₄, R₅ and R₆ taken independently are hydrogen,hydrocarbyl or substituted hydrocarbyl, C₁ to C₁₈ unsubstituted orsubstituted alkyl, unsubstituted or substituted alkenyl, unsubstitutedor substituted cycloalkyl, unsubstituted or substituted cycloalkylcontaining at least one heteroatom, unsubstituted or substituted aryl,and unsubstituted or substituted heteroaryl;

(iii) R₇ is an aromatic group having from 6 to 30 carbons, and R₈ is afully or partially reduced derivative of R₇; and

(iv) N-aryl-2-lactam (III), N-cycloalky-2-lactam (IV), or a mixturethereof, may comprise 100% by weight of the total product formed, orwherein additional products may be produced.

In addition, this invention relates to the synthesis of N-alkyl-2-lactam(VI) from a reaction between a lactone (I) and an alkyl nitro compound(V) in the presence of a catalyst and hydrogen;

wherein:

(i) n=0-11;

(ii) R₁, R₂, R₃, R₄, R₅ and R₆ taken independently are hydrogen,hydrocarbyl or substituted hydrocarbyl, C₁ to C₁₈ unsubstituted orsubstituted alkyl, unsubstituted or substituted alkenyl, unsubstitutedor substituted cycloalkyl, unsubstituted or substituted cycloalkylcontaining at least one heteroatom, unsubstituted or substituted aryl,and unsubstituted or substituted heteroaryl;

(iii) R₉ is an alkyl group having from 1 to 30 carbons, and wherein R₉may be C₁-C₃₀ unsubstituted or substituted alkyl, C₁-C₃₀ unsubstitutedor substituted alkenyl, C₁-C₃₀ unsubstituted or substituted alkynyl,C₃-C₃₀ unsubstituted or substituted cycloalkyl, or C₃-C₃₀ unsubstitutedor substituted cycloalkyl containing at least one heteroatom; and

(iv) N-alkyl-2-lactam (VI) may comprise 100% by weight of the totalproduct formed, or wherein additional products may be produced.

A catalyst, with or without a support, may be present in the processesof the invention to effect the amination reactions. A promoter mayoptionally be used to aid the reactions. The promoter can be a metal.

The processes of the present invention may be carried out in batch,sequential batch (i.e., a series of batch reactors) or in continuousmode in any of the equipment customarily employed for continuous process(see for example, H. S. Fogler, Elementary Chemical ReactionEngineering, Prentice-Hall, Inc., N.J., USA). The condensate waterformed as the product of the reaction is removed by separation methodscustomarily employed for such separations, such as distillation.

A preferred embodiment of the invention is one in which n=1 to 7, andR₁, R₂, R₃, R₄, R₅ and R₆ taken independently are hydrogen or alkyl. Amore preferred embodiment is one in which n=1, R₅ is hydrogen or methyl,and R₁, R₂, R₃, R₄, and R₆ are hydrogen.

The aryl and cycloalkyl groups represented by R₇ and R₈ preferably havefrom 6 to 30 carbons. More preferably, the aryl and cycloalkyl groupsrepresented by R₇ and R₈ have from 6 to 12 carbons. The unsubstituted orsubstituted alkyl or cycloalkyl group represented by R₉ preferably hasfrom 1 to 30 carbons. More preferably the unsubstituted or substitutedalkyl or cycloalkyl group represented by R₉ has from 1 to 12 carbons.

In the processes of the invention, a molar ratio of aryl or alkyl nitrocompound to lactone of from about 0.01/1 to about 100/1 is preferred atthe start of the reaction. A molar ratio of aryl or alkyl nitro compoundto lactone of from about 0.1/1 to about 10/1 is further preferred at thestart of the reaction.

A temperature range of from about 50° C. to about 350° C. is preferredfor the processes of the invention. A temperature range of from about75° C. to about 300° C. is further preferred.

A pressure range of from about 0.3 MPa to about 20 MPa is employed forthe processes of the invention. A pressure range of from about 1.3 MPato about 7.6 MPa is preferred.

The reactions of the present invention can be performed in non-reactingsolvent media such as water, alcohols, ethers, and lactams.Alternatively, the excess of aryl or alkyl nitro compound can also actas the solvent medium.

The catalyst useful in the invention is a substance that affects therate of the reaction but not the reaction equilibrium, and emerges fromthe process chemically unchanged. A chemical promoter generally augmentsthe activity of a catalyst. The promoter herein may be incorporated intothe catalyst during any step in the chemical processing of the catalystconstituent. The chemical promoter generally enhances the physical orchemical function of the catalyst agent, but can also be added to retardundesirable side reactions.

The processes of the invention involve reductive amination of lactoneswith aryl or alkyl nitro compounds, which is effected in the presence ofa catalyst. The principal component of the catalyst useful herein isselected from metals from the group consisting of palladium, ruthenium,rhenium, rhodium, iridium, platinum, nickel, cobalt, copper, iron,osmium; compounds thereof; and combinations thereof.

A promoter may be used optionally in the reactions of the presentinvention. The promoter herein may be incorporated into the catalystduring any step in the chemical processing of the catalyst constituent.Suitable promoters for the processes of the invention include metalsselected from tin, zinc, copper, gold, silver, and combinations thereof.The preferred metal promoter is tin. Other promoters that can be usedare elements selected from Group 1 and Group 2 of the Periodic Table.

The catalyst used in the process may be supported or unsupported. Asupported catalyst is one in which the active catalyst agent isdeposited on a support material by a number of methods, such asspraying, soaking or physical mixing, followed by drying, calcination,and if necessary, activation through methods such as reduction oroxidation. Materials frequently used as a support are porous solids withhigh total surface areas (external and internal) which can provide highconcentrations of active sites per unit weight of catalyst. The catalystsupport may enhance the function of the catalyst agent. A supportedmetal catalyst is a supported catalyst in which the catalyst agent is ametal.

A catalyst that is not supported on a catalyst support material is anunsupported catalyst. An unsupported catalyst may be platinum black or aRaney catalyst. The term “Raney catalyst” as used herein refers tocatalysts that have a high surface area due to selectively leaching analloy containing the active metal(s) and a leachable metal (usuallyaluminum). The term Raney catalyst is not meant to denote any particularsource of the material. Raney catalysts have high activity due to thehigher specific area and allow the use of lower temperatures inhydrogenation reactions. The active metals of Raney catalysts includenickel, copper, cobalt, iron, rhodium, ruthenium, rhenium, osmium,iridium, platinum, palladium; compounds thereof; and combinationsthereof.

Promoter metals may also be added to the base Raney metals to affectselectivity and/or activity of the Raney catalyst. Promoter metals forRaney catalysts may be selected from transition metals from Groups IIIAthrough VIIIA, IB and IIB of the Periodic Table of the Elements.Examples of promoter metals include chromium, molybdenum, platinum,rhodium, ruthenium, osmium, and palladium, typically at about 2% byweight of the total metal.

The catalyst support useful herein can be any solid, inert substanceincluding, but not limited to, oxides such as silica, alumina andtitania; barium sulfate; calcium carbonate; and carbons. The catalystsupport can be in the form of powder, granules, pellets, or the like.

A preferred support material of the invention is selected from the groupconsisting of carbon, alumina, silica, silica-alumina, silica-titania,titania, titania-alumina, barium sulfate, calcium carbonate, strontiumcarbonate, compounds thereof and combinations thereof. Supported metalcatalysts can also have supporting materials made from one or morecompounds. More preferred supports are alumina, silica, titania andcarbon. Further preferred supports are carbons with a surface areagreater than 100 m²/g. A further preferred support is carbon with asurface area greater than 200 m²/g. Preferably, the carbon has an ashcontent that is less than 5% by weight of the catalyst support; the ashcontent is the inorganic residue (expressed as a percentage of theoriginal weight of the carbon) which remains after incineration of thecarbon.

Commercially available carbons which may be used in this inventioninclude those sold under the following trademarks: Bameby & Sutcliffe™,Darco™, Nuchar™, Columbia JXN™, Columbia LCK™, Calgon PCB™, Calgon BPL™,Westvaco™, Norit™ and Barnaby Cheny NB™. The carbon can also becommercially available carbon such as Calsicat C, Sibunit C, or Calgon C(commercially available under the registered trademark Centaur®).

In the processes of the invention, the preferred content of the metalcatalyst in the supported catalyst is from about 0.1% to about 20% ofthe supported catalyst based on metal catalyst weight plus the supportweight. A more preferred metal catalyst content range is from about 1%to about 10% of the supported catalyst. A further preferred metalcatalyst content range is from about 3% to about 7% of the supportedcatalyst.

Combinations of catalyst and support system may include any one of themetals referred to herein with any of the supports referred to herein.Preferred combinations of catalyst and support include palladium oncarbon, palladium on calcium carbonate, palladium on barium sulfate,palladium on alumina, palladium on silica, palladium on titania,platinum on carbon, platinum on alumina, platinum on silica, iridium onsilica, iridium on carbon, iridium on alumina, rhodium on carbon,rhodium on silica, rhodium on alumina, nickel on carbon, nickel onalumina, nickel on silica, rhenium on carbon, rhenium on silica, rheniumon alumina, ruthenium on carbon, ruthenium on alumina, ruthenium onsilica and combinations thereof.

Further preferred combinations of catalyst and support include palladiumon carbon, palladium on titania, platinum on carbon, iridium on carbon,rhodium on carbon, ruthenium on carbon, rhenium on carbon andcombinations thereof.

The compounds produced by the processes of the current invention displayproperties that are useful in diverse applications. N-alkyl pyrrolidoneswith alkyl chains up to about 8 carbons function as aprotic chemicalsolvents with a lower toxicity profile than other solvents. The carbonchains of N-lower pyrrolidones are not long enough to allow micelleformation in water; thus these compounds do not exhibit significantsurfactant properties. N-alkyl pyrrolidones with alkyl groups of aboutC₈ to C₁₄ exhibit surfactant properties, and pyrrolidones with longerN-alkyl chains act as complexing agents. The surface active propertiesof alkyl pyrrolidones, such as solubility, wetting, viscosity building,emulsifying and complexing are described in U.S. Pat. No. 5,294,644.N-alkyl pyrrolidones can also be used for concentrating colloidalparticles. Due to their solvent, surfactant and complexing properties,pyrrolidones are very useful in the manufacture of pharmaceuticals,personal care products, and industrial, agricultural and householdchemicals and products.

The lactams produced by the processes of the invention are useful inpreparing pharmaceutical products for use on humans, animals, reptiles,and fish. The pyrrolidones disclosed herein are particularly useful intopical formulations, such as ointments, creams, lotions, pastes, gels,sprays, aerosols, lotions, shampoos, foams, creams, gels, ointments,salves, milks, sticks, sprays, balms, emulsions, powders, solid orliquid soaps, or oils. Pyrrolidones, such as 5-methyl-2-pyrrolidones,can be used to enhance the transdermal penetration of active componentsinto human or animal tissues and systems. Pyrrolidones can also act assolubilizers to enhance the solubility of a therapeutic agent in thecarrier system.

The pyrrolidones produced by the processes of the invention may also beincorporated into matrix systems, such as patches, for the transdermaladministration of, for example, an antimicrobial, a hormone, or ananti-inflammatory. The methods of preparation of pharmaceuticalcompositions as are commonly practiced in the pharmaceutical industryare useful with the processes of the invention. For discussion of suchmethods, see, for example, Remington's Pharmaceutical Sciences (ARGennaro, ed., 20^(th) Edition, 2000, Williams & Wilkins, PA)incorporated herein by reference.

The pyrrolidones made by the processes of the invention may be used assolvents or surfactants in liquid, gel or aerosol cleaning compositionsfor cleaning a wide range of surfaces, including textiles, such asclothing, fabrics and carpets, and hard surfaces, such as glass, metal,ceramics, porcelain, synthetic plastics and vitreous enamel. Thepyrrolidones may also be used in formulations for disinfecting hardsurfaces, such as in the household, or in institutional or hospitalenvironments, or the surface of skin, or fabric surfaces, or in the foodpreparation, restaurant or hotel industries. In addition, cleaningcompositions are useful for the removal of industrial soils, such asdirt, grease, oil, ink and the like. The pyrrolidones may also be usedas solvents in compositions for cleaning, solvating, and/or removingplastic resins or polymers from manufactured articles or manufacturingequipment.

In addition to pyrrolidones, other components may be included incleaning compositions. These additional components include nonionicsurfactants, anionic surfactants, cationic surfactants, amphotericsurfactants and solvents. Illustrative nonionic surfactants are alkylpolyglycosides, such as Glucopon (Henkel Corporation), ethylene oxideand mixed ethylene oxide/propylene oxide adducts of alkylphenols, theethylene oxide and mixed ethylene oxide/propylene oxide adducts of longchain alcohols or of fatty acids, mixed ethylene oxide/propylene oxideblock copolymers, esters of fatty acids and hydrophilic alcohols, suchas sorbitan monooleate, alkanolamides, and the like.

Illustrative anionic surfactants are the soaps, higher alkylbenzenesulfonates containing from 9 to 16 carbons in the higher alkyl group ina straight or branched chain, C₈-C₁₅ alkyl toluene sulfonates, C₈-C₁₅alkyl phenol sulfonates, olefin sulfonates, paraffin sulfonates, alcoholand alcoholether sulfates, phosphate esters, and the like.

Illustrative cationic surfactants include amines, amine oxides,alkylamine ethoxylates, ethylenediamine alkoxylates such as theTetronic® series from BASF Corporation, quaternary ammonium salts, andthe like.

Illustrative amphoteric surfactants are those which have both acidic andbasic groups in their structure, such as amino and carboxyl radicals oramino and sulfonic radicals, or amine oxides and the like. Suitableamphoteric surfactants include betaines, sulfobetaines, imidazolines,and the like.

Illustrative solvents include glycols, glycol ethers, aliphaticalcohols, alkanolamines, pyrrolidones and water.

Such surfactants and solvents are described, for example, inMcCutcheon's (2002), Volume 1 (Emulsifiers and Detergents) and Volume 2(Functional Materials), The Manufacturing Confectioner Publishing Co.,Glen Rock, N.J.

Cleaning compositions may also include additional components, such aschelating agents, corrosion inhibitors, antimicrobial compounds,buffering and pH adjusting agents, fragrances or perfumes, dyes, enzymesand bleaching agents.

N-alkyl-2-pyrrolidones are useful in cleaning and stripping formulationswhich are used to remove (or strip) a photoresist film (or other similarorganic polymeric material film) or layer from a substrate, or to removeor clean various types of plasma-etch residues from a substrate.N-alkyl-2-pyrrolidones are also useful as surfactants in cleaningformulations for removing solder pastes from printing applicators andcircuit assemblies.

N-alkyl-2-pyrrolidones, such as 5-methyl-N-octyl-2-pyrrolidone and5-methyl-N-dodecyl-2-pyrrolidone, may be included as components in inkjet inks in order to improve resistance to highlighter smear whenprinted into an image, lead to an even print (minimize the degree ofbanding) and impart an improved waterfast resistance and/or a better dryor wet rub property. 2-Pyrrolidones, such as5-methyl-N-cyclohexyl-2-pyrrolidone or 5-methyl-N-methyl-2-pyrrolidone,may also be used as a solvent in the preparation of hot melt or phasechange inks for color printing.

The pyrrolidones made by the processes of the invention can also beutilized in the manufacture of agrochemicals, including but not limitedto herbicides, insecticides, fungicides, bactericides, nematicides,algicides, mulluscicides, virucides, compounds inducing resistance toplants, repellants of birds, animals and insects, and plant growthregulators, or mixtures thereof. The method of manufacture comprisescontacting an agrochemically effective agent as known to persons skilledin the art with at least one of the pyrrolidones produced by any of themethods of the invention. The agrochemical composition can optionallycomprise additional auxilary components as are commonly used in theagrochemical industry.

Pyrrolidones, such as 5-methyl-N-methyl pyrrolidone and5-methyl-N-cyclohexyl pyrrolidone, can be used as water insoluble polarco-solvents to solubilize water insoluble pesticides and otheragrochemicals and increase the effective amount of active ingredient.N-alkyl pyrrolidones, preferably N-C₃₋₁₅ alkyl pyrrolidones, inparticular 5-methyl-N-octyl pyrrolidone and5-methyl-N-dodecylpyrrolidone, can be used as nonionic surfactants thataid as emulsifiers. Plant growth regulators are used to improve theeconomic yield of agricultural plants. 5-Methyl-N-octyl pyrrolidone and5-methyl-N-dodecyl pyrrolidone can be utilized as solvents in emulsionscontaining plant growth regulators.

In addition, pyrrolidones can be utilized in liquid or aerosolformulations for dermal application of insect repellants by humans;examples include mosquito and tick repellants. Manufacture of suchinsect repellants comprises, contacting an effective amount of at leastone insect repelling agent with at least one product produced using atleast one process of the invention.

Pyrrolidones, such as 5-methyl-N-methyl-2-pyrrolidone, can also be usedin antimicrobial formulations for the preservation of animal silage.5-Methyl-N-alkyl-2-pyrrolidones can also be used as part of a moreenvironmentally-conscious method for drycleaning clothing that includesa surfactant and densified carbon dioxide in place of traditionalsolvents.

In addition, 5-methyl-2-pyrrolidones can be used as components in aprotective composition for use on painted surfaces, such as cars. Thepyrrolidones function to wet the surface and promote spreadibility ofthe protectant.

Different plastic materials are often not miscible, resulting inproducts that exhibit insufficient mechanical properties. Monomeric andpolymeric 5-methyl-pyrrolidone-containing compounds can be used ascompatibilizers for plastic compositions; the compatibilizers attachthemselves to the interface between the polymers involved, or penetrateinto the polymers, thereby improving the adhesion between the polymersand enhancing mechanical properties.

5-Methyl-N-pyrrolidones can also be used as compatibilizers in therefrigeration and air conditioning industries. Transitioning fromchlorofluorocarbon to hydrofluorocarbon refrigerants has necessitatedthe use of a new class of lubricants due to immiscibility withconventional lubricants such as mineral oil, poly α-olefin andalkylbenzene. However the new class of lubricants is expensive and alsovery hygroscopic. Absorption of water leads to acid formation andcorrosion of the refrigeration system, as well as the formation ofsludges. The lack of solubility of the hydrofluorocarbons in theconventional lubricants results in a highly viscous lubricant in thenoncompressor zones, and results in insufficient lubricant return to thecompressor. This can eventually result in a number of problems,including the compressor overheating and seizing and insufficient heattransfer in the refrigeration system. Compatibilizers solubilize thepolar halogenated hydrocarbon refrigerant and the conventional non-polarlubricant in the non-compressor zones, which results in efficient returnof lubricant to the compressor zone. Compatibilizers may include the5-methyl-N-alkyl- and 5-methyl-N-cycloalkyl-2-pyrrolidones.

Pyrrolidones can also be used as fuel and lubricant additives. Forexample, N-alkyl-2-pyrrolidones can be used as detergents anddispersants in fuel additive compositions to keep valves, carburetorsand injection systems clean, thereby improving the combustioncharacteristics and reducing deposits, thus reducing air pollutingemissions. In addition, 5-methy-N-methyl-2-pyrrolidone can be used toremove unsaturated hydrocarbons from raw lube distillates or deasphaltedresidual lube stocks to produce solvent-refined base oils as lubricants.

Methods for the preparation of cleaning, stripping, agrochemical andplastic formulations are well known to persons skilled in the art.Similarly, methods for the preparation of insect repellants, ink jetinks, protective formulations for paint, fuel additives and lubricants,refrigeration and air conditioning lubricants, and for dry cleaning arewell known in the art. Pyrrolidones can act as solvents, surfactants,dispersants, detergents, emulsifiers, viscosity builders and complexingagents in these formulations. Appropriate pyrrolidones are selectedbased on standard screening procedures for product performance.Additional components, such as pharmaceutical or agrochemical activeagents or colorants, may be added to specific formulations as the mainfunctional component; the nature of the functional component orcomponents would be determined by the specific use. Auxiliarycomponents, which enhance or are critical to the efficacy of theformulation, may also be added. Auxiliary components may includesolvents or cosolvents, thickeners, antioxidants, spreading agents,preservatives, adhesives, emulsifiers, defoamers, humectants,dispersants, surfactants, suitable carriers, matrix systems, deliveryvehicles, fragrances, salts, esters, amides, alcohols, ethers, ketones,acids, bases, alkanes, silicone, evaporation modifiers, paraffins,aliphatic or aromatic hydrocarbons, chelating agents, gases foraerosols, propellants or for dry cleaning, oils and water. Appropriateauxiliary components for the uses described herein are known to personsskilled in the art.

The following examples are illustrative of the invention. Examples 1 to10 are actual examples; Examples 11 to 16 are prophetic.

EXAMPLES

The following abbreviations are used:

ESCAT-XXX: Series of catalysts provided by Engelhard Corp. (Iselin,N.J.)

Calsicat Carbon: Catalyst support from Engelhard Corp. (lot S-96-140)

JM-XXXX: Series of catalysts from Johnson Matthey, Inc. (W. Deptford,N.J.)

ST-XXXX-SA: Series of catalysts from Strem Chemicals (Newburyport,Mass.)

SCCM: Standard cubic centimeters per minute

GC: Gas chromatography

GC-MS: Gas chromatography-mass spectrometry

For catalyst preparation a commercially available support such ascarbon, alumina, silica, silica-alumina or titania was impregnated byincipient wetness with a metal salt. The catalyst precursors used wereNiCl₂.6H₂O (Alfa Chemical Co., Ward Hill, Mass.), Re₂O₇ (Alfa ChemicalCo.), PdCl₂ (Affa Chemical Co.), IrCl₃.3H₂O (Alfa Chemical Co.),RuCl₃.xH₂O (Aldrich Chemical Co., Milwaukee, Wis.), H₂PtCl₆ (JohnsonMatthey, Inc.), RhCl₃.xH₂O (Alfa Chemical Co.) and IrCl₃.3H₂O (AlfaChemical Co.). The samples were dried and reduced at 300-450° C. underH₂ for 2 hours.

Raney catalysts are available from W.R. Grace & Co. (Columbia, Md.).Butyrolactone, valerolactone, nitropropane, nitrobenzene and dioxane areavailable from Fisher Scientific (Chicago, Ill.).

Catalyst Preparation: 5% Pt on Acid Washed Calsicat Carbon

In a 150 ml beaker, a solution was made up of 4.5 ml 0.3 M H₂PtCl₆ with4.0 ml deionized H₂O. To the beaker were added 4.75 g Qalsicat AcidWashed Carbon (12×20 mesh, dried at 120° C. overnight). The slurry wasallowed to stand at room temperature for 1 hr with occasional stirring,followed by drying at 120° C. overnight with frequent stirring (untilfree flowing).

In an alumina boat, in a quartz lined tube furnace, the catalyst waspurged with 500 SCCM N₂ at room temperature for 15 min and then with 100SCCM He at room temperature for 15 min. The catalyst was heated to 150°C. and held at 150° C. under He for 1 hr. At this point, 100 SCCM H₂were added and the sample was held at 150° C. under He and H₂ for 1 hr.The temperature was increased to 300° C. and the catalyst was reduced at300° C. under He-H₂ for 8 hrs. The H₂ was stopped, the sample was heldat 300° C. under He for 30 min and then cooled to room temperature inflowing He. The catalyst was finally passivated in 1.5% 02 in N₂ at 500SCCM for 1 hr at room temperature and weighed 4.93 g when unloaded.

Additional catalysts used in the present invention were preparedfollowing a similar procedure.

Batch Reduction of Gamma Valerolactone to 5-Methyl-N-Aryl-2-Pyrrolidoneand 5-Methyl-N-Cycloalkyl-2-Pyrrolidone

To a 5 ml pressure vessel was added 50 gm of catalyst, and 1 gm of asolution containing 30 wt % gamma valerolactone, 37% aryl nitro compoundand 33% dioxane. The vessel was sealed, charged with 5.52 MPa hydrogenand heated to 225° C. for 4 hours. The pressure was maintained at 5.52MPa during the course of the reaction. At the end of the reaction, thevessel was rapidly cooled in ice, vented and an internal GC standard ofmethoxyethylether was added. The solution was separated by pipette fromthe catalyst and analyzed by GC-MS using an HP 6890 (Agilent; Palo Alto,Calif.) equipped with a FFAP 7717 (30 meter) column. The results setforth in the tables below are based on area %.

The examples described below were performed according to a similarprocedure under the conditions indicated for each example.

Examples 1-6 Preparation of 5-Methyl-N-Pronyl-2-Pyrrolidone (PrP) byBatch Reduction of Butyrolactone (BL) Using Nitropropane (NP) as theAlkyl Nitro Compound

The reactions were carried out for 4 hrs. at a temperature and pressureof 150° C. and 5.52 MPa, respectively. The feedstock wasbutyrolactone/nitropropane/dioxane at a ratio (weight %) of 40/21/39.The results are set forth in the following table.

Ex. BL Conversion PrMP No. Catalyst/Support^(a) (%) Selectivity (%) 1 5%Pd/C (ESCAT- 83.1 92.5 142) 2 5% Pt/C ESCAT- 79.2 89.7 248) 3 5% Ru/C(ST- 99.7 30.5 141060-SA) 4 5% Rh/C (JM- 100.0 65.1 11761) 5 5% Re/C(Fisher) 9.9 0.0 6 5% Ir/Calsicat C 79.6 75.0 ^(a)Source forcommercially available catalyst/support is in parentheses.

Examples 7-10 Preparation of 5-Methyl-N-Phenyl-2-Pyrrolidone (PhMP) and5-Methyl-N-Cyclohexyl-2-Pyrrolidone (CHMP) by Batch Reduction ofValerolactone (VL) Using Nitrobenzene (NB) as the Aryl Nitro Compound

The reactions were carried out for 4 hrs. at a temperature and pressureof 225° C. and 5.52 MPa, respectively. The feedstock wasvaerolactone/nitrobenzene/dioxane at a ratio (weight %) of 30/37/33. Theresults are set forth in the following table.

VL PhMP CHMP Ex. Conversion Selectivity Selectivity No.Catalyst/Support^(a) (%) (%) (%) 7 5% Pd/C (ESCAT- 16.0 1.5 27.9 142) 85% Pt/C (ESCAT- 8.8 25.2 31.1 248) 9 5% Rh/C (JM-11761) 14.1 3.6 45.0 105% Ru/C (ESCAT- 73.3 0.4 26.5 440) ^(a)Source for commercially availablecatalyst/support is in parentheses.

Example 11 Pharmaceutical Formulations

A) Topical Formulation: Solubilizer (diethylene glycol monoethyl ether)2% to 50% Skin permeation enhancer 2% to 50%(N-hydroxyethyl-2-pyrrolidone) Emulsifier 2% to 20% Emollient (propyleneglycol) 2% to 20% Preservative 0.01 to 0.2% Active agent 0 to 25%Carrier Balance B) Cream: Phase 1: Polyethylene glycol and ethyleneglycol 5% palmitostearate Caprilic/capric triglycerides 5% Oleoylmacrogolglycerides (Labrafil M 1944CS) 4% Cetyl alcohol 5.5% PPG-2myristyl ether propionate (Crodamol PMP) 6%5-methyl-N-hydroxyethyl-2-pyrrolidone 2% Phase 2: Xanthan gum 0.3%Purified water 55% Phase 3: Propylene glycol 1% Methylparaben 0.18%Propylparaben 0.02% Phase 4: Naftifine hydrochloride (antifungal) 1%Diethylene glycol monoethyl ether (Transcutol) 15%

Procedure:

Xanthan gum is dispersed in water and allowed to stand. Phase 1components and phase 2 components are separately heated to 75° C.; phase1 is mixed into phase 2 under high speed agitation. The temperature ismaintained at 75° C. while stirring for 10 min. The mixture is thenslowly cooled while stirring at low speed. At 40° C., phase 3 is added.Naftifine is then mixed well into the Transcutol, and the mixture isadded to the cream, mixed well and the cream is cooled to roomtemperature.

C) Transdermal Patch Formulation: Ketoprofen 0.3%   Polysorbate 800.5%   5-Methyl-N-methyl-2-pyrrolidone 1% 5-Methyl-N-ethyl-2-pyrrolidone2% PEG 400 10%  CMC-Na 4% Na-polyacrylate 5.5%   Sanwet 1M-1000PS 0.5%  Polyvinyl alcohol 1% PVP/VA copolymer 3%

Example 12 Cleaning Compositions

A) Grease Removal Formulation: Water 89%  Potassium carbonate 1%Potassium bicarbonate 5% 5-Methyl-N-octyl-2-pyrrolidone 2.5%  Deriphatec 151-C (Henkel Corp.) 2.5%   B) Oil-in-Water Emulsion inAerosol Form: Crillet 45 (Croda) 3.30%   Monamulse DL 1273 (MonaIndustries, Inc.) 3.30%   5-Methyl-N-dodecyl-2-pyrrolidone 5.50%  Denatured absolute ethanol 100 AG/F3 (CSR Ltd.) 15.40%    Norpar 15(Exxon) 5.50%   Deionized water 44.10%    Butane 16.95%    Propane5.95%   C) All-Purpose Liquid Cleaning Composition: Neodol 91-8 (Shell)3.5%   Linear alkyl (C9-13) benzene sulfonate, Mg salt 10.5%   Propyleneglycol mono-t-butyl ether 4.0%   Coco fatty acid 1.4%  5-Methyl-N-decyl-2-pyrrolidone 1.0%   Magnesium sulfate heptahydrate5.0%   Water 74.6 D) Shower-Rinsing Composition: Glucopon 225 (HenkelCorp.) 2.0%   Isopropyl alcohol 2.2%   Sequestrene 40 (45%, Ciba) 1.0%  Fragrance 0.02%   Barquat 4250Z (50% Lonza) 0.2%  5-Methyl-N-octyl-2-pyrrolidone 1.0%   Water 93.58%    E) DishwashingComposition: Ethanol (95%) 8.6%   Alfonic 1412-A [Ethylene oxide sulfate(59.3%)] 22.5%   Alfonic 1412-10 1.1%   Sodium chloride 0.9%  5-Methyl-N-decyl-2-pyrrolidone 7.5%   Water 59.4%   F) AqueousAntimicrobial Cleaning Composition: Adipic acid 0.40%   Dacpon 27-23 AL(Condea; C₁₂₋₁₄ sodium alkyl 0.15%   sulfate, 28% active) Isopropylalcohol 1.8%   Dowanol PnB (Dow; propylene glycol 0.30%   mono-N-butylether) 5-Methyl-N-octyl-2-pyrrolidone 0.4%   Sodium hydroxide 0.05%  Water 96.9%  

An antimicrobial wipe can be made by impregnating a substrate with theabove composition; the substrate can be spunlace comprisingviscoselpolyester at a ratio of 70:30 with a specific weight of 50grams/m². The composition to substrate ratio is about 2.6:1.

G) Disinfectant: Benzalkonium chloride 5% Sodium carbonate 2% Sodiumcitrate 1.5% Nonoxynol 10 2.5% 5-Methyl-N-octyl-2-pyrrolidone 5% Water84% H) Anti-Parasitidal Agent (for dermal application to animals):Antiparasital agent 1 to 20% 5-Methyl-N-isopropyl-2-pyrrolidone 30%Benzyl alcohol (preservative) 3% Thickener 0.025-10% Colorant 0.025-10%Emulsifier 0.025-10% Water Balance

Example 13 Stripping/Cleaning Formulation

5-Methyl-N-methyl-2-pyrrolidone 30% Monoethanolamine 55% Lactic acid  5%Water 10%

Example 14 Ink Jet Ink

CAB-O-JET 300 (Active)   4% Diethylene glycol 17.5%5-Methyl-N-octyl-2-pyrrolidone  2.5% Deionized H₂O   76%

Example 15 Agrochemical Compositions

A) Composition for the Control of Insects: Permethrin 2%5-Methyl-N-decyl-2-pyrrolidone 3% Dimethyl dipropyl naphthalene 7%Lauryl alcohol 5% Hymal 1071 (Matsumoto Yushi Seiyaky, Inc.) 10% Hytenol N-08 (Daiichi Kogyo Seiyaku, Inc.) 2% Polyoxyethylene glycol71%  B) Pesticide Formulation: 5-Methyl-N-alkyl pyrrolidone 48%  Sodiumdodecyl sulfate 12%  Agrimer AL25 10%  Rodeo (pesticide; Monsanto) 1%Water 29%  C) Emulsifiable Fungicide Formulation: Kresoxin-methyl 0.5%  Propylene carbonate 1.5%   Aromatic petroleum distillate 150 (Exxon)2.9%   5-methyl-N-octyl-2-pyrrolidone 3.8%   CaH/DDBSA [50% (Cadodecylbenzene 1.4%   Sulfonate + Dodecylbenzene Sulfonic acid (5:1) inExxon 150 Water Balance

Example 16 Formulation for Protective Composition for Painted AutomobileSurfaces

Propylene glycol phenyl ether 2.0% 5-Methyl-N-octyl-2-pyrrolidone 0.1%Emulsified silicone: 3.0% a) dimethyl silicone (2.67%) b)amino-functional silicone (0.21%) c) silicone resin (0.12%) Water 94.9% 

What is claimed is:
 1. A process for preparing a reaction productcomprising N-aryl-2-lactam (III), N-cycloalkyl-2-lactam (IV), or amixture thereof, which comprises the step of contacting a lactone (I)with an aryl nitro compound (II) in the presence of hydrogen gas and acatalyst, the catalyst being optionally supported on a catalyst support,and, optionally, said contacting is performed in the presence of asolvent;

wherein: (i) n=-11; (ii) R₁, R₂, R₃, R₄, R₅ and R₆ taken independentlyare hydrogen, hydrocarbyl or substituted hydrocarbyl, C₁ to C₁₈unsubstituted or substituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted cycloalkyl, unsubstituted orsubstituted cycloalkyl containing at least one heteroatom, unsubstitutedor substituted aryl, and unsubstituted or substituted heteroaryl; and(iii) R₇ is an aromatic group having from 6 to 30 carbons, and R₈ is afully or partially reduced derivative of R₇.
 2. A process for preparinga reaction product comprising N-alkyl-2-lactam (VI), the processcomprising the step of contacting a lactone (I) with an alkyl nitrocompound (V) in the presence of hydrogen gas and a catalyst, thecatalyst being optionally supported on a catalyst support, and,optionally, said contacting is performed in the presence of a solvent;

wherein: (i) n=0-11; (ii) R₁, R₂, R₃, R₄, R₅ and R₆ taken independentlyare hydrogen, hydrocarbyl or substituted hydrocarbyl, C₁ to C₁₈unsubstituted or substituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted cycloalkyl, unsubstituted orsubstituted cycloalkyl containing at least one heteroatom, unsubstitutedor substituted aryl, and unsubstituted or substituted heteroaryl; and(iii) R₉ is an alkyl group having from 1 to 30 carbons, and wherein R₉may be C₁-C₃₀ unsubstituted or substituted alkyl, C₂-C₃₀ unsubstitutedalkenyl, C₂-C₃₀ unsubstituted or substituted alkynyl C₃-C₃₀unsubstituted or substituted cycloalkyl, or C₃-C₃₀ unsubstituted orsubstituted cycloalkyl containing at least one heteroatom.
 3. Theprocess as recited in claim 1 or 2, wherein the catalyst is selectedfrom metals selected from the group consisting of nickel, copper,cobalt, iron, rhodium, ruthenium, rhenium, osmium, iridium, platinum,palladium, at least one Raney metal; compounds thereof; and combinationsthereof.
 4. The process as recited in claim 3, wherein the catalyst ispalladium and compounds thereof.
 5. The process as recited in claim 3,wherein the catalyst is supported to form a supported metal catalyst andthe content of the metal in the supported metal catalyst is from 0.1% to20% by weight.
 6. The process as recited in claim 1 or 2, wherein thecatalyst support is selected from the group consisting of carbon,alumina, silica, silica-alumina, silica-titania, titania,titania-alumina, barium sulfate, calcium carbonate, strontium carbonate,compounds thereof, and combinations thereof.
 7. The process as recitedin claim 6, wherein the carbon has an ash content, the ash content beingless than about 5% by weight of the catalyst support, and optionallywherein the carbon has a surface area of more than about 200 m²/g. 8.The process as recited in claim 1 or 2, wherein the process isoptionally performed in the presense of a promoter.
 9. The process asrecited in claim 1 or 2, wherein n=1-7, and R₁, R₂, R₃, R₄, R₅ and R₆taken independently are hydrogen or alkyl.
 10. The process as recited inclaim 1 or 2, wherein n=1, R₅ is hydrogen or methyl, and R₁, R₂, R₃, R₄and R₆ taken independently are hydrogen.
 11. The process as recited inclaim 1, wherein R₇ is an aromatic group having 6 to 12 carbons and R₈is a cycloalkyl group having 6 to 12 carbons.
 12. The process as recitedin claim 9 or 10, wherein R₇ is an aromatic group having 6 to 12 carbonsand R₈ is a cycloalkyl group having 6 to 12 carbons.
 13. The process asrecited in claim 2, wherein R₉ is an alkyl or cycloalkyl group havingfrom 1 to 12 carbons.
 14. The process as recited in claim 9 or 10,wherein R₉ is an alkyl or cycloalkyl group having from 1 to 12 carbons.15. The process as recited in claim 1 or 2, wherein the compoundrepresented by Formula (II) or Formula (V) and the compound representedby Formula (I) are in a molar ratio of from about 0.01/1 to about 100/1at the start of the reaction.
 16. The process as recited in claim 15,wherein the reaction is performed at a temperature of from about 50° C.to about 350° C.
 17. The process as recited in claim 15, wherein thereaction is performed at a hydrogen pressure of from about 0.3 MPa toabout 20 MPa.
 18. The process as recited in claim 5, wherein thesupported metal catalyst is selected from the group consisting ofpalladium on carbon, palladium on calcium carbonate, palladium on bariumsulfate, palladium on alumina, palladium on titania, platinum on carbon,platinum on alumina, platinum on silica, iridium on silica, iridium oncarbon, iridium on alumina, rhodium on carbon, rhodium on silica,rhodium on alumina, nickel on carbon, nickel on alumina, nickel onsilica, rhenium on carbon, rhenium on silica, rhenium on alumina,ruthenium on carbon, ruthenium on alumina and ruthenium on silica. 19.The process as recited in claim 18, wherein the supported metal catalystis selected from the group consisting of palladium on carbon, palladiumon titania, platinum oh carbon, rhodium on carbon, rhenium on carbon,ruthenium on carbon and iridium on carbon, and combinations thereof. 20.The process as recited in claim 1 or 2, wherein the solvent medium forthe reaction is selected from the group consisting of water, alcohols,ethers, nitro compounds of Formula (II) or Formula (V), lactams, and thereaction product of claim 1 or 2, respectively.
 21. The process asrecited in claim 2, wherein n=1, R₅ is hydrogen or methyl, and R₁, R₂,R₃, R₄ and R₆ taken independently are hydrogen, wherein R₉ is an alkylgroup having from 1 to 12 carbons or a cycloalkyl group having from 6 to12 carbons, wherein the catalyst is supported and the supported catalystis palladium on carbon or palladium on titania, and wherein thetemperature of the reaction is from about 75° C. to 300° C. and thepressure of the reaction is from about 1.3 MPa to about 7.6 MPa.
 22. Aprocess for preparing a pharmaceutical composition, the processcomprising the steps of: i) preparing N-alkyl-2-lactam (VI) using aprocess comprising the step of contacting a lactone (I) with an alkylnitro compound (V) in the presence of hydrogen gas and a metal catalyst,the metal catalyst being optionally supported, and, optionally, in thepresence of a solvent;

 wherein: (a) n=0-11; (b) R₁, R₂, R₃, R₄, R₅ and R₆ taken independentlyare hydrogen, hydrocarbyl or substituted hydrocarbyl, C₁ to C₁₈unsubstituted or substituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted cycloalkyl, unsubstituted orsubstituted cycloalkyl containing at least one heteroatom, unsubstitutedor substituted aryl, and unsubstituted or substituted heteroaryl; (c) R₉is an alkyl group having from 1 to 30 carbons, and wherein R₉ may beC₁-C₃₀ unsubstituted or substituted alkyl C₂-C₃₀ unsubstituted orsubstituted alkenyl, C₂-C₃₀ unsubstituted or substituted alkynyl C₃-C₃₀unsubstituted or substituted cycloalkyl, or C₃-C₃₀ unsubstituted orsubstituted cycloalkyl containing at least one heteroatom; and ii)contacting N-alkyl-2-lactam (VI) with at least one pharmaceuticallytherapeutic agent.
 23. A process for preparing an agrochemicalcomposition, the process comprising the steps of: i) preparingN-alkyl-2-lactam (VI) using a process comprising the step of contactinga lactone (I) with an alkyl nitro compound (V) in the presence ofhydrogen gas and a metal catalyst, the metal catalyst being optionallysupported, and, optionally, in the presence of a solvent;

 wherein: (a) n=0-11; (b) R₁, R₂, R₃, R₄, R₅ and R₆ taken independentlyare hydrogen, hydrocarbyl or substituted hydrocarbyl, C₁ to C₁₈unsubstituted or substituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted cycloalkyl, unsubstituted orsubstituted cycloalkyl containing at least one heteroatom, unsubstitutedor substituted aryl, and unsubstituted or substituted heteroaryl; (c) R₉is an alkyl group having from 1 to 30 carbons, and wherein R₉ may beC₁-C₃₀ unsubstituted or substituted alkyl C₂-C₃₀ unsubstituted orsubstituted alkenyl, C₂-C₃₀ unsubstituted or substituted alkynyl C₃-C₃₀unsubstituted or substituted cycloalkyl, or C₃-C₃₀ unsubstituted orsubstituted cycloalkyl containing at least one heteroatom; and ii)contacting N-alkyl-2-lactam (VI) with at least one agrochemicallyeffective agent.